Manufacture of modified organic isocolloid materials



Patented June 10, 1941 MANUFACTURE OF MODIFIED ORGANIC ISOCOLLOIDMATERIALS Laszl After, Mansfield, Mass., asslgnor to J. Randolph Newman,Washington, D. 0., as

trustee No Drawing. Application January 31, 1938, Se-

rial No. 188,014.

16 Claims.

This invention relates to the manufacture of modified organic isocolloidmaterials and it comprises methods of making such modified products fromorganic isocolloid materials containing a relatively high concentrationof dispersed phase, such as partially bodied fatty oils, etc., wherein aminor amount of a modifying agent or polar compound, advantageously anorganic polar compound, is colloidally dispersed or dissolved in suchorganic isocolloid to modify the physical and other properties thereof,such as melting point, viscosity, state of aggregation, solubility,etc., suificient polar compound being employed to alter one or more ofsaid properties of the organic isocolloid material and said dispersionand modification being usually effected with the aid of heat, in theabsence or presence of suit- In Hungary May 19, 1926 able solvents, andwherein the modified products so obtained are sometimes subsequentlyvulcanized, emulsified, etc., to further modify their properties; and italso comprises the modified organic isocolloids so obtained, all as morefully hereinafter set forth and as claimed.

In my prior applications, I have described processes for modifying thephysical and other properties of organic isocolloids. This applicationis a continuation in part of my prior applications; the various organicisocolloids and polar compounds or modifying agents and the severalprocedures disclosed in such applications being useful in the presentinvention.

This application is a continuation-in-part of my prior applicationSerial No. 466,587 filed July 8, 1930, which issued February 1, 1938, asPatent No. 2,106,708. That prior application, in turn, is acontinuation-in-part of my application Serial No. 143,786 filed October23, 1926 (now Patent No. 2,189,772), and of the variouscontinuations-in-part of that parent application, particularly, SerialNo. 359,425, filed April 30, 1929.

The said parent application and the said continuations-in-part, togetherwith the patents which have issued upon the same, are set forth in thefollowing Table A:

Table A Serial No. Filed l Patent No. Issued Feb. 13, 1940 4461174:466,587 July loidally dispersing various modifying agents in organicisocolloid materials, I obtain modified products having altered physicalproperties, etc., which are useful in the commercial and industrialarts. The modifying agents are employed in minor amounts and are organicand inorganic compounds which are electrolytes or polar compoundscapable of influencing the modification of the isocolloid substances. Inthose applications many illustrative examples of the practice of mygeneric invention or discovery are disclosed. In most cases,particularly when the polar compound used as the modifying agent is aninorganic salt, the mixture of the organic isocolloid such as a fattyoil, and the modifying agent were heated to relatively high temperaturessuch as 250 to 350 C. to obtain highly modified products; the heating tosuch temperatures increasing the concentration of dispersed phase of theisocolloid and causing the polar compound to become associated with thedispersed phase.

The present invention is based upon my further discovery that when anorganic isocolloid containing a relatively high concentration ofdispersed phase is employed as the starting material in any of my priorprocesses, the desired modification is more readily and quicklyobtained, even at lower temperatures 'or in a shorter time or both inmany cases. In some cases with the dispersed phase in satisfactoryconcentration in such organic isocolloids, a simple dispersion of themodifying agent therein causes the desired changes in the physicalproperties of the starting material. That discovery and methods ofapplying the same are generically and specifically disclosed in myapplication Ser. No. 466,587 of which the present application is acontinuation-in-part.

And in my Ser. No. 466,587 (now Patent-No. 2,106,708), I havegenerically and specifically disclosed methods of modifying organicisocolloids wherein organic isocolloids having a relatively highconcentration of dispersed phase, are modified with a modifying agentcapable 'of facilitating the hodying of said organic isocolloids and ofmodifying the properties thereof. And in that application, such methodsare generically claimed; and specifically those in which a' metal saltis used as the modifying agent.

The present application also relates to methods of modifying organicisocolloids similar to those disclosed and claimed in Ser. No. 466,587and it is directed to such methods wherein the said modifying agent is ametal-free organic polar compound.

And as shown in my Ser. No. 466,587 and earlier applications, by myprior investigations, I have made important discoveries. I havediscovered that various oils, such as fatty oils, etc., and many otherorganic materials, both natural and artiflcial, are really organicisocolloids. That is, they comprise a dispersion medium and a dispersedphase which are chemically similar. In such isocolloids, the physicalproperties thereof are in part dependent upon the relation between thephases thereof. Thus two materials having approximately the samechemical composition might have quite difierent physical properties. Ihave also discovered that polar compounds are capable of influencing therelations between those phases of these organic isocolioids and that thephysical and other properties of these organic isocolloids, such asmelting point, viscosity, solubility, film strength, etc., are alteredby dispersing or dissolving a polar compound in the organic isocolloid.They impart polarity to the isocolloid system thus modifying it. Thesegeneric discoveries and methods of modifying the physical properties oforganic isocolloids with polar compounds as the modifying agent, basedon those discoveries, are set forth in prior copending applications setforth ante.

As disclosed in those applications, my generic method for modifying theproperties of organic isocolloids comprises dissolving or colloidallydispersing a minor amount of a polar compound in the organic isocolloid,the amount of polar compound b'eing suflicient to substantially alterone or more of its properties. Generally from 1 to 30 per cent of thepolar compound by weight on the organic isocolloid is used,advantageously from 2 to per cent in most cases, particularly with fattyoils such as linseed oil and the like. With mineral oils, sometimes lessthan 1 per cent of certain polar compounds gives desirable improvementsin the oil. Various methods may be used to disperse the polar compoundin the isocolloid to be modified, so long as the polar compound becomesdispersed therein in complete (molecular or colloidal) solution.

In some cases, as disclosed in Serial No. 143,786, the polar compoundand organic isocolloid may be mixed cold to produce the modifiedproducts. That is, the materials can be simply stirred or agitatedtogether at room temperature, if'the polar compound is directly solubleat low temperatures in the organic isocolloid to be modified. Suchmixing at room temperature may also be accomplished by the use ofappropriate solvents; solvents capable of dissolving both the organicisocolloid and the polar compound used. In such methods, sufficientcommon solvent to blend the materials into a homogeneous mass may beemployed and the solvent subsequently removed by evaporation if desired.Again, the polar compound and organic isocolloid may be melted together,as also disclosed in Ser. No. 143,786. 'Ihat is, heated to a temperaturesufiicient to fuse them into a homogeneous mass. Such fusing .or meltingtogether, may be employed when the polar compound or organic isocolloidor both are solids which fuse or melt at moderate temperatures and whichare readily miscible with each other. In such cases, warming or heatingto fusion temperature, advantageously with stirring or agitation, untila homogeneous mass is obtained gives useful products.

Generally, in order to insure complete dissolution or dispersion of thepolar compound in the organic isocolloid, the operations should becarried out under the application of heat. The degree of heat requireddepends on the nature of the isocolloid material being modified and themodifying agent or polar compound used in a given case. In thosemethods, wherein the mixture is heated to elevated temperature todisperse those polar compounds which are more dimcult to dissolve incentain organic isocolloids, the range of temperatures employed isgenerally from 100 to 800 0., usually from 200' to 300 C. Onlyoccasionally is a higher temperature necessary, say as high as 350 C.The heat treatment promotes the complete (molecular or colloidal)dissolution of the polar compound in the substance to be treated andmodified. In some cases, it is advisable to continue the heat treatmentafter the dissolution or dispersion of the polar compound issubstantially complete. Thus, for instance, when the isocolloid materialbeing modifled is a fatty oil and the agent is dispersed in it at 200 C.or above, continued heating produces a fargoing heat-bodying of the oiland in this way it is possible to produce relatively hard, solidproducts when desired. Such methods are disclosed in my application Ser.No. 359,425 and other continuations of Ser. No. 143,786, .manyillustrative examples being' given in which both inorganic and organicpolar compounds are used as the modifying agents for the organicisocolloids. As stated in my application Ser. No. 359,425, theeffectiveness of my modifying agents (polar compounds) is appreciablygreater when applied in the colloidal condition and as there disclosed,they may be incorporated and dispersed in the starting material (organicisocolloid to be modified) by means of suitable mills; that is, thepolar compound or modifying agent may be milled into the organicisocolloid in the usual mixers or mills, suflicient heat being appliedto promote milling and mixing. For instance, a temperature of C. may beused for mixing, as mentioned in my Ser. No. 359,425 and the mixturethen subjected to higher temperatures to 180 C. or higher), if desiredor necessary to obtain further modification of the orga cisocolloid.

her, as set forth in those applications, I have found that theproperties of the products obtained by my methods can be influenced bythe nature and physical condition of the gas present in contactwith thematerial undergoing treatment. That is, by varying the pressure thespeciilc nature of the products can be somewhat changed. These processescan be efl'ected under reduced, atmospheric or increased pressure.Sometimes, the mixture of polar compound and organic isocolloid may beheated under increased pressure and then the pressure subsequentlyreleased forreduced. This may be advantageously used when solvents areemployed as mentioned ante; the solvent being retained at the highpressure and removed when the pressure is released or reduced, that issubsequently removed by distll lation from the hot mass. Generallyspeaking, the rariiication of the gas present during the treatmentintensifies the actions in these processes'lhus in many cases, theheating is effected under vacuum or reduced pressure. Likewise, thepresence of air or other gas somewhat altersthe' results obtained. IWhen a'gas treatment is employed in conjunction with the heathis, thegas is usually blown or passed through the heated mixture. For thesepurposes non.- oxidizing gases, such as $02, CO2, nitrogen, etc., areadvantageous. Also the gas may be developed in situ, from compound suchas peroxides, carbonates, sulphides, sulphites and the like, to give thecorresponding gas, according to the conditions employed.

Likewise the modifying agent or polar compound may be produced in situwithin the organic isocolloid material during the heating, by

using compounds which react, under-the condi-' tions employed, to formthe desired modifying agent.

Also, in modifying these organic isocolloids, true or colloidalsolutions of one or more polar compounds or electrolytes in an organicsolvent may be used to incorporate them into the substance to bemodified.

Having summarized the procedural steps of the methods of practicing mygeneric invention as disclosed in the said prior applications, thevarious types of polar compounds advantageous in such methods are nextsummarized. As stated in Ser. No. 143,786 and Ser. No. 359,425 and thecontinuations thereof, the following classes of polar compounds ormodifying agents are typical:

Metal salts, particularly those of alkali metals,

alkaline earth metals, zinc, magnesium, etc. Salts of organic acids.Salts of inorganic acids, particularly sulphites,

sulphides, carbonates, etc. Mixtures of metal salts and metal peroxides.Organic acids. Aromatic. Aliphatic. Organic bases.

Amines. Hydroxy compounds (phenols, etc.). Organic compounds containingboth an acidic inorganic residue and an organic residue.

Organic halogen compounds.

Aromatic. Aliphatic. Organic sulphonic acids and their esters. Organicsulphonyl chlorides. Organic esters of inorganic acids. Inorganic saltsof organic bases. Nitro compounds. Diphenyl sulphides and sulphones(organic sulphides, etc.) Metallo-organic compounds.

Metal alcoholates. Aryl metal compounds.

The above general classes of polar compounds. useful as modifying agentsin the practice of my generic invention, are fully illustrated byspecific typical compounds in my various prior aphigh concentration ofdispersed phase; according to my further discovery that such organicisocolloids are more readily and easily modified ,by such polarcompounds and procedures.

As most of the natural organic isocolloids, such as linseed o l and manyother fatty oils. in the natural or refined condition, only contain arelatively low concentration of dispersed phase, I usually employ in thepresent invention, an organic isocolloid, the concentration of thedispersed phase of which has been increased by known or other suitablemeans. such as partiall bodied fatty oils, etc.; although other organicisocolloids, either natural or artificial. having a high concentrationof dispersed phase may be employed if desired. I

Thus in the usual practice of the present in vention, I ordinarilyemploy a new two step method to modify these organic isocolloids,

namely, methods which comprise first increasing the concentration of thedispersed phase to a suitable degree by known procedures and thereafterdispersing the modifying agent or polar compound in such materials. Bythis combination of steps. improved results are obtained. In suchmethods, I may employ the modifying agents and other details shown in myprior applications in practicing the second step of the new processes.However, in the general practice of the present invention, I may use anynatural or artificial organic isocolloid which already has a suitablehigh concentration of the dispersed phase, this being the maindistinction of the present invention.

This distinction is clearly shown by a comparison of some of my priormethods with the present improvement wherein certain advantageousresults are obtained. In my prior methods, in cases where theconcentration of the dispersed phase of the isocolloid is comparativelysmall, such as in linseed oil, in addition to'the dispersion of themodifying agent or polar compound, an increase in the concentrationofthe dispersed phase is necessary in making highly modified productssuch as solidified oils. For instance, in modifying linseed oil withinorganic agents, such as metal salts, by my prior methods, 'thedispersion of those agents in the oil and the increase in theconcentration of the dispersed phase of the oilare effected side by sidein the same heat treatment. In such methods, as illustrated in Ser. No.143,786, the mixture of linseed oil and metal salt is heated to between300-350 C. for several hours. In other words. when an inorganic agent isused with such oils, long heating at high temperatures is necessary todisperse them in the oil. Further, such temperatures are sufiicient toheat-body the oil, and as disclosed in my Ser. No. 359,425, it isadvantageous to continue the heating after the polar compound hasdissolved to obtain highly modified products. In this way, theconcentration of the dispersed phase is simultaneously increased in theheat treatment used to disperse the inorganic modifying agent or polarcompound. However, long heating at high temperatures tends to causediscoloration of the oil, that is, darkening of the product. This isprobably due to charring of small particles of the oil, caused by-localoverheating. On the other hand, in many industrial applications, it isvery desirable that the modified isocolloids have a light color.

My investigation seeking improvements in this direction lead to myfurther discovery set forth ante, namely, that isocolloids containinghigher concentrations of dispersed phase are more readily modified withthe aid of polar compounds. For instance, with organic isocolloidscontaining the dispersed phase in a satisfactory concentration, a simpledispersion of these modifying agents or polar compounds can produce thedesired changes in the physical properties thereof. Also, themodification of such isocolloids can be efiected at much lowertemperatures, such as to 250 0., than is the case of organic isocolloidscontaining a low concentration of dispersed phase.

As stated ante, partially bodied or thickened oils are suitable asstarting material in my improved processes as they contain the dispersedphase in a relatively high concentration.

Such thickened fatty oils are well known in the art and may be obtainedin several ways which are likewise well known methods of thickening orbodying such oils. The following are typical examples of thickened fattyoils of particular types and of the methods of preparing them:

1. Uviol oil, obtained by treating the oil with ultra-violet rays.

2. Oxidized oils or air-blown oils, obtained by blowing air or oxygenover or through the oilv to be thickened, either at room or elevatedtempera'tures.

3. Blown oils, non-oxidized, obtained by blowing gases such as carbondioxide, nitrogen, hydrogen, sulphur dioxide, hydrogen sulphide, etc.,through the oil to be thickened and bodied at room temperature orelevated temperatures, elevated temperatures such as 200 C. or above,usually being employed in making this class of thickened oils.

4. Stand oil (heat-bodied or polymerized oil), obtained by heating theoils in an ordinary atmosphere at elevated temperatures for a long time.

Polymerized oils (4) are heat-bodied oils produced by heatingunsaturated fatty oils to polymerizing temperatures, 200 C. and above,for seveal hous until a thickened, viscous, heat-bodied oil product isobtained. They are also known as stand oil. This method is well known inthe art and these heat-bodied oils are a distinct type of commercial oilproducts. different from oxidized oils or air-blown oils (class 2 ante).

In my present process any of these partially bodied oils, obtained byknown methods, and containing a relatively high concentration ofdispersed phase may be used.

Thus in my new two step methods of making modified, bodied fatty oilproducts, I may employ various fatty oils capable of being bodied, suchas disclosed in my prior applications acknowledged ante, and increasethe concentration of the dispersed phase by known methods and thereaftermodify the partially bodied oil with the polar compounds also disclosedin those applications. For instance the fatty oils disclosed in Ser. No.143,786 and Ser. No. 359,425 may be used in these two step methods.Among the suitable fatty oils are linseed oil, rapeseed oil, Perillaoil, soya bean oil, poppyseed oil, sunflower oil, cottonseed oil, fishoils, such as menhaden oil, etc., (train oils), pineseed oil, corn oil,olive oil, castor oil, etc. That is, vegetable and animal, includingmarine -.animal, oils are generally useful in these methods.

Also esters of the fatty acids derived from such oils, other than thenatural glycerides thereof may be employed here.

Any of the above oils, etc., may be heat-bodied in the first step of thepresent invention and then treated with polar compounds to producevaluable modified, heat-bodied products. Likewise, they can be partiallybodied by other methods and then further treated in the second step withpolar compounds. In the second step of any of these methods, the variouspolar compounds disclosed in my prior applications may be used.

These polar compounds may be classified in various ways, according tothe groups present in the molecule. The following is one broadclassification of such compounds, as are useful in the presentinvention: metal salts of inorganic acids, metal salts of organic acids,organic salts of organic acids, organic salts of inorganic acids,organic bases, organic acids, inorganic acids, organic halogencompounds, organic nitro com- They are somewhat pounds, organicsulphides and sulphones, and metallo-organic compounds.

As stated in the parent application Ser. No. 143,786, the electrolytesor polar compounds useful in the practice of my inventions may be salts,as well as acids and organic metal compounds. In the practice of thepresent invention or improvement, such compounds containing thefollowing cations or anions or both, are advantageous:

As cations-Ammonium, sodium, potassium, lithium, strontium, calcium,barium, magnesium, iron (ferric and ferrous), aluminum, cobalt, lead,antimony, manganese, tin (stannic and stannous), cadmium, bismuth, zinc,and organic ammonium ions, etc.

As anions.Naphthalene sulphonic (acid) carbonic (acid), tartaric (acid),oxalic (acid), acetic (acid), formic (acid), hydrochloric (acid),hydrobromic (acid), hydroiodic (HI) (acid), sulphuric (acid), sulphurous(acid), hydrosulphuric (acid), thiosulphuric (acid), nitric (acid),nitrous (acid), citric (acid), hydrocyanic (acid), thiocyanic (acid)maleic (acid), salicyclic (acid) sulphanilic (acid), and naphthenic(acid), etc.

Thus salts of inorganic and of organic acids may be used; both aromaticand aliphatic organic acids. Some of these are salts of monobasic acidsand some are salts of polybasic acids, particularly dibasic acids. Bothneutral and acid salts may be used. Likewise, both of the acidsthemselves and their anhydrides may be employed as the modifying agentin this invention. Hydroxy-acids and unsaturated acids and their saltsare also useful here.

In the present invention, the salts of weak acids with alkali metals,with alkaline earth metals, with zinc and with magnesium, such as theirsulphides, sulphites and carbonates, are advantageous, particularly inmodifying heat-bodied fatty oils. Some of those advantageous methods areclaimed in my copending application Ser. No. 466,587; this applicationbeing a continuation of that application.

This application is primarily directed to the use of organic modifyingagents or polar compounds which are fusible and/or soluble at lowertemperatures and of other readily soluble polar compounds. Such organicpolar compounds or modifying agents disclosed and fully illustrated inmy prior applications, Ser. No. 143,786, Ser. No. 359,425, Ser. No.446,170, and Ser. No. 446,172, and in the application Ser. No. 446,173filed by myself and one Lajos Susztek, now Patent No. 1,963,065. Thevarious classes of such polar compounds and many specific examplesthereof are given post.

Also in Ser. No. 359,425, I have given other examples of metal saltswhich are advantageous in the practice of the present invention. Some ofthese are: ammonium iodide, magnesium sulphate, magnesium chloride, zinccarbonate, zinc bromide, sodium sulphide, barium sulphide, bariumthiocyanate, lead chromate, potassium dichromate, cadmium sulphide,sodium bicarbon ate, lithium sulphite, .tin carbonate, tin sulphite, tinsulphide, antimony sulphide, zinc sulphide, barium sulphide, bariumcarbonate, calcium sulphite, strontium sulphite, magnesium sulphite,barium sulphite, lead sulphite, cadmium sulphite, mercuric sulphate,sodium 2:628 naphthylamine disulphonate, sodium 2:6:8 naphtholdisulphonate,sodium 1 8:3 6 aminonaphthol disulphonate, sodium 1:5naphtholsulphonate, sodium 3:3:6 naphthol disulphonate, and sodium 2:6naphthol sulphonate. In addition to these, other salts of .shown ante.

organic acids may be used, such as salts of allphatic and aromaticcarboxylic acids; for in-, stance tartrates, citrates, salicylates, etc.as Generally organic salts are more soluble or miscible with organicisocolloids, such as fatty oils, etc.

Thus an advantageous class of polar compounds useful ln the presentinvention are the organic esters of inorganic acids, both aryl andalk'yl esters. The following are illustrative of this class: triphenylphosphate, tricresyl phosphate and other alkyl-phenyl phosphates,nitrocresyl carbonate, ethyl chlorosulphonate, and dimethyl sulphate. Inaddition to these, other alkyl and aryl esters of inorganic acids, suchas borates, phosphates, sulphides, sulphates, thiocyanates, etc., may beused; for instance, propyl, butyl, amyl esters. Likewise, esters ofvarious aliphatic alcohols and phenols with organic acids may beemployed as shown post.

Still another class of modifying agents or polar compounds useful inthis invention are the inorganic salts of organic bases; of which thefollowing compounds are illustrative: m-nltroaniline hydrochloride,diphenylamine hydrochloride, diphenylamine hydrobromide,trichloroaniline hydrochloride, diphenylamine sulphate, diaminodiphenylsulphate, aniline sulphate, and amino-azo-benzene sulphate.

Several of the above compounds in addition to being salts, contain othergroups which impart polarity to the compound, such as nitro, aminoandhalogen groups. Compounds containing such groups are useful per se inthis invention as polar compounds or modifying agents as shown post,

As examples illustrative of organic salts of organic acids, there may bementioned diphenylamine trichloroacetate and methyl p-toluenesulphonate. Other wholly organic salts inay be used. For instance, thealkyl and aryl esters of the various acids mentioned ante, such astartrates, oxalates, acetates, formates, thiocyanates, salicylates,etc., may be used in the present invention. These are illustrative ofthe esters of monoand di-basic acids which may be employed. Likewise,alkyl and phenyl esters of other aliphatic and aromatic carboxycyli'cacids, both of mono-basic and dibasic acids, such as phthalates,benzoates, acetates, abeitates, oleates, stearates, laurates,palmitates, ricinoleates, etc., may be used. Both the monoand (ii-esters of di-basic acids are useful here. Likewise mixed alkyl andaryl ester can be employed in some cases. Typical examples are asfollows: di butyl phthalate, mono-butyl phthalate, di-ethyl phthalate,ethyl-butyl phthalate, di-phenyl phthalate, ethyl-phenyl tartrate,methyl abietate, ethyl abietate, di-ethyl succinate, phenyl thiocyanate,ethyl malonate, diethylammonium diethyldithiocarbamate, ethylsalicylate, ethyl ether of ethyl salicylate, and butyl ether of ethylricinoleate. That is ether ester and acid esters may be also employedhere. Further thioesters, such as diaminodiphenyl sulphide, may also beused; they being so to speak organic esters of organic mercaptans (RS-H)which are more or less sulphur acids. Other useful organic sulphides arediphenyl sulphide, ethyl phenyl sulphide and the alkyl thioethers ofnitrobenzenes, such as ethyl thioether of 2-nitrobenzene or of 2:4dinitrobenzene. That is the phenyl group of such sulphides may befurther substituted with groups such as amino, nitro, etc.;

these groups increasing the polarity of the molecule.

In fact, nitro compounds per se are advantageous in the practice of thepresent invention, as is illustrative in the specific examples givenpost.

As examples of nitro organic compounds, here useful as the polarcompound or modifying agent, the following are typical: o-nitrophenol,p-nitrophenol, nitrobenzene, dinitrobenzene, dinitroaniline, p-nitroacetanilide, nitrocresol carbonate, and m-nitroaniline hydrochloride.These illustrate the various general types of compounds that may beused, in addition to the nitro compounds shown in other classificationsof the polar compounds here useful.

The nitro compounds are but one type of the organic polar compoundswhich I may use as modifying agents in the present methods. I havefound, as stated in my prior applications, that they and other polarcompounds which contain an organic residue and an inorganic acidicresidue, are generally useful as modifying agents for these purposes. Byan inorganic acidic residue, I mean such an inorganic residue as can beconverted, by the addition of one or more hydrogen atoms into aninorganic acid. Such organic polar compounds may be represented by thefollowing generic formula:

wherein A represents the organic residue and X represents the acidicinorganic residue. The acidic inorganic groups may be nitro, sulphurcontaining radicles, halogen, etc. and one or more such groups may bepresent in the molecule and attached to the organic residue.

One advantageous class of these organic polar compounds are the organichalogen compounds, both aromatic and aliphatic, containing chlorine,iodine, bromine, etc. and illustrative compounds of this class are givenpost.

The following compounds are typical halogenated organic polar compoundsand may be used in the practice of this invention: o-dichlorobenzene,p-dichlorobenzene, trichlorobenzene,

. nitro-chlorobenzenes, ortho, meta and para, ni-

tro-dichlorobenzene, chloro-dinitrobenzene, nitrochloro-phenol,chlorotoluene, chloroxylene, chlorophenol, naphthalene tetrachloride,naphthalene trichloride, naphthalene hexochloride, naphthalenemonochloride, chlorinated diphenyl, monochlorobenzene, pinenehydrochloride, l-chloro-oanisidine, p-nitro-chloro-benzene,triphenyl-chloro-methane, diphenyl-dichloro methane, benzyl chloride,benzoyl chloride, acetyl chloride, acetyl bromide, acetyl iodide,phthaloyl chloride, propionyl' chloride, butanoyl chloride, chloralhydrate, trichloroacetic acid, monochloroacetic acid, m-nitroanilinehydrochloride, diphenylamine hydrochloride, diphenylaminetrichloroacetate, trichloroaniline hydrochloride, diphenylaminehydrobrornide, iodoform, 2:5 dichlorbenzene sulphonic acid, benzenesulphonyl chloride, p-toluene sulphonyl chloride,naphthalene-l-sulphonyl chloride, and ethylchlorsulphonate.

In lieu of the above compounds, other halogenated aryl compounds,aliphatic chlorides, acyl chlorides, chloroacids, hydrochloride salts,etc., may be used. here.

From the above list, it is clear that many of the organic halogencompounds contain other substituents in addition to the halogen, such ashydroxy, amino, nitro, alkyl, aryl, and other groups. Therefore they maybe classified in other groupings of these modifying agents. Like- .wise,it is clear that the organic halogen comwherein R represents an arylnucleus, X represents hydrogen, chlorine or an alkyl group or a metaland n is to 4. Typical examples of such compounds are the followingcompounds:

benzene sulphonic acid, p-toluene sulphonic acid, 2:5 dichlorobenzenesulphonic acid, m-xylidine sulphonic acid, p-toluidine-m-sulphonic acid,naphthalene 2:6 sulphonic acid, beta-naphthol 1 :5 sulphonic acid,beta-naphthol 3:6:8 sulphonic acid, beta-naphthylamine 3:6:8trisulphonic acid, 2:1 naphthylamine sulphonic acid, 2:6 naphthylaminesulphonic acid, 2-phenylamine-8-naphthol-6-sulphonic acid,methyl-p-toluene sulphonate, ethyl chlorosulphonate, benzene sulphonylchloride, p-toluene sulphonyl chloride, naphthalene-l-sulphonylchloride, diniethyl sulphate, diaminodiphenyl sulphide, diaminodiphenylsulphone, nitrophenyl ethyl sulphide, diaminodihydroxy anthraquinonedisulphonic acid, and

diaminotetrahydroxyanthraquinone disulphonic acid. Metal salts of suchsulphonic acids have been shown ante, such as the sodium salts, etc.,and all of these compounds are useful here in the present methods.

Many of the polar compounds illustrated ante in the variousclassifications also contain amine or amino groups. In the presentinvention amine compounds as a class are useful. My prior applicationSer. No. 446,170 is primarly directed to modifying organic isocolloidswith amine compounds as the polar compound. As there disclosed, amineshaving a relatively high molecular weight are advantageous; particularlyaromatic amines such as monoand di-amines of naphthalenes, etc., anddiamines of phenylene, diphenyl and such compounds. This application isa continuation in part of my Ser. No. 446,170. In the present invention,as in the methods of that prior application, compounds containingprimary, secondary or tertiary amine groups and containing two or moreamine groups may be used as the modifying agent. The following aminecompounds are typical examples of this class of modifying agent:

Mono-aromatic amines:

Alpha naphthylamine beta naphthylamine,

and Napththylamine also containing sulphonic, hydroxy, and othersubstituent groups in the molecule, as shown ante and post. Phenylenediamines H2N--RNH2I Para-phenylene diamine Ortho phenylene diamine Metaphenylene diamine Para-tolylene diamine Diphenyl diamines H2NR-RNH2:

Benzidine Dianisidine Diphenyl diamines of complex structure having.

the two phenyl groups connected with a bridge" linkage.

HaN-R-X-R-NHz:

pp-diamino-diphenyl methane (X CH2) pp-diamino-diphenyl ether (X 0)pp-diamino-diphenyl sulphide (X S) pp-diamino-diphenyl amine (X NH)pp-diamino-diphenyl urea (X NH- (JO-NH) pp-diamino-diphenyl thiourea (XHN- CSNH) pp-diamino-diphenyl benzophenone (X pp-diamino-diaphenylguanidine (X HNCNNH) It is to be noted that in some of these compoundssulphur or oxygen are present in the molecule in addition to the aminegroups. Some contain secondary amine groups in addition to the primaryamine group. In addition to these, amines of even more complex stucturemay be used.

, The following are illustrative of such compounds: 1:4diaminoanthraquinone, diamino dihydroxy anthraquinone disulphonic acid,diamino tetrahydroxy anthraquinone disulphonic acid, p-diamino-dimethylcarbazole, diaminodiphenazine, diaminofuchronimine,mercaptobenzthiazole, piperidine pentamethylenedithiocarbamate,heptaldehydeaniline, diphenylguanidine, tolylguanidine, andamine-aldehyde condensation products. 7

In many of these diamines the two amine groups are joined by an aromaticnucleus com-- prising one or more phenyl groups, the general formulabeing HzN-Q-NH: wherein Q is an aromatic group.

One of the advantages of the amines as modifying agents is that they arerelatively easier to dissolve or disperse in fatty oil and otherisocolloids to modify them.

The amines may be used by themselves or in conjunction with othermodifying agents, etc. in modifying organic isocolloid materialsaccording to the present invention. For instance, the amines may be usedin con-Junction with compounds comprising within the molecule an acidicinorganic residue and an organic residue, such as given ante. Sometimesthey may also be used with certain auxiliary materials, as shown in Ser.No. 446,170 and other copending applications of mine. Again, it issometimes advantageous to use as the modifying agent an organic polarcompound containing both an amine group and an acidic residue, such asthe amino-aromatic sulphonic acids and other compounds of that typeshown ante.

Ser. No. 446,170 is specifically directed to methods wherein a fatty oilis mixed with a small amount, usually 1 to 10 per cent of an amine ofhigh molecular weight and the mixture heated to 200 C. or above, until asolidified oil product is obtained on cooling. As shown in thatapplication, using a stand 011 as the starting material gives animproved process and product. The present application is directed to thelatter method and as to this, it is a continuation in part of Ser. No.466,170.

In addition to the amines shown in Ser. No. 446,170 and thosementionedante, I may also use other organic bases as the modifying agentin the present processes. Many such organic bases are disclosed in myprior applications; for instance,

naphthols, phenols, etc. of some examples have been already given here.

The following compounds are typical of the organic bases useful inmodifying organic isocolloids by the present methods: o-nitrophenol,p-nitrophenol, dinitroaniline, alpha-naphthol, phenol, cresol, xylol,pyrogallol, dihydroxybenzene, glycerol, quinoline,diaminodiphenylguanidine, diphenylguanidine, aminonaphthol, aminophenol,and diphenylurea. Clearly a wide range of organic bases may be used,according to the type of modified isocolloid product to be obtained froma given starting material. Also the use of aryl-hydroxy compounds, asthe modifying agent, is further illustrated by the compounds given anteunder other classification.

However, in most embodiments of the present invention, the organic basesare used in conjunction with other modifying agents, they being employedto give an additional modification in the properties of the productsobtained, as is pointed out in my prior applications Ser. No. 143,786,Ser, No. 359,425 and 359,427. The organic bases may be used here inconjunction with metal salts, acids, acid chlorides (acyl chlorides),etc., employing the proportions and procedures of my prior applications.

In fact, in the present invention acids themselves may be used alone asthe modifying agent and are an important class of polar compoundstor-use in these improved methods. Certain of the advantageous acids,particularly the organic acids, have been described ante. In connectionwith the salts and esters, I mentioned many acids and these are suitablefor use in the pounds useful in some of the present methods is theacids, particularly the organic acids. Both aromatic and aliphaticacidsmay be used. Some of these have been mentioned ante. To furtherillustrate this class and the subclasses thereof,

the following typical examples of such compounds are given: formic,acetic, monochloracetic, trichloracetic, propionic, butyric, isovaleric,capric, lauric, palmitic, oxalic, tartaric, citric, ricinoleic,crotonic, malonic, hydrooxyacetic acid, lactic, succinic, maleic, malic,benzoic, phthalic, salicylic, sulphcsalicylic, hydrocyanic, thiocyanic,sulphanilic, 2:3 hydroxynaphthoic, alpha-naphthyl sulphamic, benzenesulphonic, and the other aryl sulphonic acidsshown ante. Other similaracids may be used. Likewise, the halogen derivatives of these acids maybe employed such as the chlor-acids of which the chloracetic acids givenante are typical. Also the anhydrides and acid chlorides (acylchlorides) of the above and similar acids may be used here as themodifying agent; the acetyl and benzoic chlorides also shown ante beingtypical examples. As already shown salts of these acids, both metal andorganic salts, may be used as the polar compound here.

Sometimes it is advantageous to form the polar compound in situ in theorganic isocolloid being modified in the present methods as was done insome of my prior processes, using two agents which can react to form thedesired polar compound in situ; This is possible when acyl chloride areused in conjunction with certain other compounds or secondary agents,such as organic bases and metallo-organic compounds; examples of thelatter being shown in my Ser. No. 273,159. Those metallo-organiccompounds, such as metal alcoholates of aliphatic alcohols and ofphenols and metal aryl compounds are themselves polar compounds and areuseful here asmodifying agents, as shown post. Likewise, inorganic polarcompounds may be formed in situ in the material being modified in thepresent processes using the methods shown in my prior applications, suchas Ser. No. 359,425 and the other applications filed simultaneouslytherewith.

Generally, I find it is sometimes advantageous with use in conjunctionwith the primary modifying agent or polar compound, another compoundwhich I term auxiliary agents or sensitisers. That is, I have furtherfound that in the present methods that the dissolution of theelectrolytes or polar compounds in the starting materials (iso'colloids)and the modification processes are facilitated by the addition of theso-called auxiliary or sensitizing/agents. These fall into two groups,namely the purely inorganic agents, such as silica gel, fullers earth,etc., and the purely organic agents, of typical examples orillustrations are given post. For instance, silica gel or fullers earthmay be admixed with metal salts, particularly acid salts, or'acids,etc., or impregnated with solutions of these polar compounds and dried,and such mixtures used to effect the modification of the isocolloid inlieu of the polar compound alone. In this way, the action is expedited,particularly with fatty oils. As to the purely organic agents useful assensitisers or auxiliary agents, I may mention the following:formaldehyde and other. aldehydes, hexamethylenetetramine,thiocarbanilide, phthalamide; benzidine and other amines; phenol andother aryl hydroxy compounds; alpha naphthol, 2:3 hydroxynaphtholicacid, quinoline, pyrogallol, glycerol, benzene, and other volatilesolvents. The specific examples of auxiliary agents mentioned above areto be taken as typical of the substances which have been successfullyused for this purpose and not as comprising all the effective substanceswhich may be used. In fact, some of those substances are themselvespolar compounds. That is I may use one of the polar compounds to serveas an auxiliary agent for another one of them, used as the primarymodifying agent. Some further examples of polar compounds which are alsouseful in the present methods as auxiliary agents or sensitisers, are asfollows: amino-azoloenzene sulphate, aniline sulphate, dimethylsulphate, nitrocresyl carbonate, triphenyl phosphate, t-ricresylPhosphate, pale cresylic acid, trichloracetic acid, benzene sulphonicacid, m-xylylidinesulphonic acid, beta-naphthylamine-G:B-disulphonicacid, beta-naphthyl amine-G-sulphonic acid, 2:6 naphthalene disulphonicacid, aminosalicylic acid, oxalic acid, formic acid, naphthalenesulphochloride, acetyl chloride, pinene hydrochloride, chloral hydrate,naphthalene tetrachloride, i o d o f o r m, o-dichlorbenzene.p-dichlorbenzene, monochlorbenzene, trichlorbenzene, diphenylaminehydrobromide, and p-nitroacetanilide. For instance, the dissolution of 5per cent of sodium bisulphite or other salt in linseed stand oil isfacilitated by the addition of 2 per cent of any of the above auxiliaryagents or sensitisers, t0 the mixture prior to the heating. Also in thisway a lighter colored product is obtained. As the amount of metal saltis varied, the percentage of auxiliary agent may also be varied. Thatis, using 10 per cent of polar compound instead of per cent, the amountof auxiliary agent may likewise be increased say to 4 per cent. Further,the ratio of polar compound to auxiliary agent can also be varied; theamount of auxiliary agent may be larger or smaller than that of thepolar compound, according to the results sought. Thus, there are severalways of carrying out the present invention, according to the polarcompound and procedure selected from those shown in my priorapplications, or according to the way in which the concentration of thedispersed phase of the organic isocolloid is increased prior to suchtreatments.

But generally the methods of this invention for modifying the physicalproperties (such as melting point, viscosity, solubility, state ofaggregate, film strength etc.) of organic isocolloids, comprises firstincreasing the concentration of the dispersed phase to a suitabledegree, such as by partially bodying a fatty oil, and then dispersingthe modifying agent in the material so obtained (bodied oil, etc.) withthe aid of heat, etc., to obtain improved products. In the presentmethods, I find it advantageous to employ organic polar compounds in thesecond step.

In using organic polar compounds as the modifying agent in theseprocesses, I find it is advantageous to use those having the followingformula wherein R represents an aryl residue and A, B, C and D representhydrogen or a group of the class consisting of nitro, halogen, hydroxy,amino, substituted amino, ether, thioether, carboxylic, ester,sulphonic, chlorosulphonic, sulphonate groups, at least one such groupbeing present. Advantageously two or more of such groups may be present,particularly groups which are differ-- ent from the others present. Theaminonaphthols and the aminoand amino-hydroxysulphonic acids areadvantageous polar compounds useful as modifying agents in the practiceof this invention; particularly those disclosed in my prior applicationsSer. Nos. 359,425 and 446,170, of which several typical illustrativeexamples are given ante.

Also, in the practice of the present invention, I may use metalperoxides as the modifying agent; for instance I may employ theprocedures and particular metal peroxides disclosed in my applicationsSer. No. 359,426 or Ser. No, 359,425. Again, as shown in Ser. No.359,425, the metal peroxides may be used in conjunction with metalsalts, and this is also useful in the present methods.

In the present methods, peroxides of alkali metals, such as sodium,potassium, etc., of alkaline earth metals, such as barium, calcium,magnesium, etc., and of zinc, bismuth, etc., are advantageous. They maybe advantageously employed to modify either air-blown oils or heatbodiedoil, as well as being generally useful for modifying organic isocolloidscontaining a high concentration of dispersed phase. When a heatbodiedoil is so modified, the oil products obtained are oxidized, heat-bodiedoils and have in part the properties of an oxidized oil and of aheat-bodied oil. These oil products are heavily bodied, viscous oils orthermoplastic ,various liquid As a further improvement in the presentin- I vention, volatile solvents may be employed to facilitate thedispersion of the polar compound in the organic isocolloid beingtreated. That is, I may employ solutions of the modifying agents inorganic solvents. Suitable solvents are benzol, toluol, methyl-ethylketone, ether, acetone, a mixture of ether and acetone, amyl acetate,butyl alcohol, amyl alcohol, etc. Other aromatic and aliphatichydrocarbons, ethers, ketones, esters and alcohols may be used. Eitherlowboiling or high boiling solvents may be employed according to theparticular organic isocolloid, polar compound and procedure used. Inthis way, the modifying agents can be dispersed in the isocolloid atlower temperatures, using either inorganic or organic polar compounds,the latter being the most-advantageous in such methods.

In most cases, heating the solvent-containing mixtures to between and C.gives good results. Only in a. few cases is it necessary to heat for ashort time at 200 C. The heating of such mixtures may be effected undervarious conditions of pressure, as in the direct use of the polarcompound without solvent. By heating these solvent-containing mixturesunder subatmospheric (reduced) pressure to such temperatures, all ormost of the solvent is distilled off and modified products substantiallyfree of solvent may be directly obtained. If further modification isdesired the products so obtained and containing the polar compounddispersed therein, may be further heated to obtain very highly modifiedmaterials. This further heating may be to somewhat higher temperaturesand any residual solvent may be simultaneously removed.

Again, the solvent-containing mixtures may be heated in a closed vesselunder increased pressure, until the desired modification is obtained inthe presence of the solvent and then the modified product recovered freeof solvent, by releasing the pressure. This release of pressure flashesoff the solvent and cools the modified product. Any solvent remaining inthe modified product so obtained can be removed by subsequentevaporation or distillation, if present and as desired. In such methods,the pressure during the first heating may be equal or greater than thevapor pressure of the solvent at said temperature of heating and underthe conditions for modification. In this way, the solvent is retained inthe mixture. If desired, all of the solvent may be retained in theliquid condition during the modifying treatment.

Various illustrations of the above methods, using solvent, are givenpost. In such methods, a minor amount of solvent is ordinarily used; avolume of solvent less than that of the oil or organic isocolloid. Butin some cases, greater amounts of solvent can be used.

The amount of polar compound or modifying agent used in the presentprocesses is usually less than 30 percent by weight on the oil ororganic isocolloid employed. In most cases, from 2 to 10 percent givesgood results and is used. In certain cases less than 2 percent may beused, sometimes as low as 0.5 percent.

In carrying out the processes of the present invention, all the methodsand means disclosed in my said prior applications can be used and theproducts obtained may be further modified in the various ways stated insuch prior applications for the subsequent modification of such organicisocolloid products. That is, the products obtained by the presentmethods may be further treated and modified by vulcanization,emulsification, etc., according to the methods and means given in theprior application therein acknowledged ante.

By the expression simple dispersion in the aforegoing specification notthe disappearance of a e. g. fusible modifying agent is meant but thatthe particles of the modifying agent are adsorbed by the particles ofthe material being takes a certain time, generally at least one hour andonly in exceptional cases less.

The products of the present processes are particularly useful as varnishbases, as plasticizers and as rubber compounding ingredients, either thevulcanized or unvulcanized materials.

As there are many ways of practicing the present invention and widerange of useful products can be produced by selecting the organicisocolloid, particular polar compound and details of treatment, Ipresent the following typical examples as illustrations of the practiceof this invention without any intention of being limited to the exactdetails thereof. In other words, these examples are merely illustrativeand not limitative of the present processes and products.

Example 1.This example illustrates the preparation of a heat-bodiedfatty oil suitable for modification by the present methods.

Into a suitable open kettle, there is charged 1000 lbs. of refinedlinseed oil and the oil is heated to 290-310 0.; about 2 hours beingrequired to bring the oil to that temperature. The oil is maintained atthis temperature for about 5 hours to thicken and polymerize it. Theheating is then discontinued and the oil permitted to cool. When at roomtemperature, the partially bodied oil so obtained is of medium viscosityand has a satisfactory color. It is soluble in the usual varnish andlacquer solvents.

The so bodied oil is withdrawn from the kettle and stored in suitablecontainers.

However, if desired, the second step or modification of the oil may beeffected in the same kettle in a continuous process and sometimes thisis done in the practice of this invention. In that case, the oil is notwithdrawn from the kettle, but is cooled to the desired temperature foradding the modifying agent to be used and the further treatment theneifected as described ante. 1

In the above example, the surface of the oil may be blanketed with aninert gas such as nitrogen or carbon dioxide, if desired. Also thebodying of the oil may be done in a closed kettle, advantageously underreduced pressure.

Also, a slow current of non-oxidizing gas, such as nitrogen,COz, S02,H2S, etc., may be passed into and through the oil while being heated tothicken it. Further, with closed kettles the heating may be underpressure.

In the above procedures, other fatty oils may be used in lieu of linseedoil and bodied in like treated, so that the simple dispersion always I.prevent the formation of pressure during blowing and the heated oil isblown with air in a. regular stream through the oil for about 15 hours.Upon cooling to room temperature a viscous, oxidized oil is obtained.

The blowing may be combined with a vacuum treatment or a pressuretreatment by regulating the gas inlet valve and the valve properly tochange the pressure of the gas in the kettle from atmospheric pressure.

By substituting sulphur dioxide for the air.

in the above procedure, there is obtained still another oil product; aviscous, blown, nonoxidized oil, which is also useful in the presentinvention. With sulphur dioxide higher temperatures may be used thanwith air or oxygen in so blowing the oil to thicken it; for instance,the oil may be heated to 290-310C., as shown in Example 1 ante, duringthe blowing with S02.

Example 3.'I'his example illustrates the modification of bodied oils.

To 1000 lbs. of the linseed oil obtained in Ex ample 1, there is added50 lbs. of benzenesulphonic acid and the mixture is heated to l40-l50 C.and maintained at that temperature for 2 hours. Upon cooling to roomtemperature there is obtained, a heavily bodied, viscous oil product.

The modified bodied is useful in making paints and varnishes andimproves the alkali-resistance of the coatings obtained from such paintsand varnishes.

In the above example, in lieu of benzenesulphonic acid, other organicpolar compounds may be used, such as 2:5-dichlorbenzene sulphonic acid,benzene sulphonyl chloride, p-nitrophenol, o-nitrophenol, benzidinebase, naphthalene tetrachloride, etc. Also the various other polarcompounds disclosed herein may likewise be employed in the above method.

The next example illustrates the modification of another type ofpartially bodied'fatty oil, namely the oxidized or air-blown oils.

Example 4.'To 1000 lbs. of the air-blown oil obtained in example 2,there is added 50 lbs. of p-toluene sulphonic acid and the mixture isheated to -150 C. and maintained at that temperature for 3 hours. Uponcooling to room temperature there is obtained a heavily bodied, viscousoil product.

The modified bodied oil product so obtained is useful in making paintsand varnishes and improves the resistance of their films to chemicals,such as acids, salts, etc.

If in the above example blown castor oil is used, instead of blownlinseed oil and a sulfosalicylic acid is used in lieu of the p-toluenesulphonic acid as the modifying agent, another and somewhat differentoil product is obtained. This modified bodied oil is useful'in preparingnitrocellulose lacquers. The films obtained from such lacquers haveincreased chemical resistance. The modified bodied castor oil product isa plasticizer for nitro-cellulose and the like.

oil product so obtained The following examples illustrate my processeswherein a solvent is employed as an auxiliary agent to facilitate thedispersion or dissolution of the polar compound in the organicisocolloid.

Example 5. parts of p-nitrophenol are dissolved in 22 parts of warmbenzene and the solution is mixed with 100 parts of linseed oil standoil, containing 12 parts of benzene. The mass is then heated in vacuo at120 C. until the solvent has been distilled off. The temperature is thenraised to 200 C. and the mass is maintained in vacuo for 2 hours at this.temperature. A very viscous paste is obtained.

Example 6.-5 parts of o-nitrophenol are dissolved in 7 parts of warmbenzene and the solution is mixed with 100 parts of linseed oil standoil containing 27 parts of benzene. The mass is heated as in Example 5,except that after the solvent has been distilled oil, the mass is heatedin vacuo for half an hour at 200 C. The product is a solidgel, at roomtemperature.

Erample 7.-5 parts of benzoic acid are dissolved in 30 parts of warmbenzene and the solution is mixed with 100 parts of linseed oil standoil and the mass is heated to 80 C. If the process is continued as inExample 5 and the heating at 200 C. is continued for 2 hours and twentyminutes, a thick oil is obtained.

Example 8.100 parts of linseed oil stand oil are mixed with 5 parts ofbenzene sulphonyl chloride dissolved in 5 parts benzene and the mass isheated in vacuo at a temperature of 120-130 C. for 3 hours. The productis a gelled, very viscous oil. The solvent distills 011 during theheating.

Example 9.If instead of benzene sulphonyl chloride used in Example 8, asolution of 5 parts of chlorsulphonic acid in 5 parts benzene is heatedwith the oil under similar conditions for 40 minutes at 110-125 C., asticky elastic gel will be obtained.

Example 10.If in Example 8 a solution of 5 parts of barium thiocyanatein 10 parts of methyl ethyl ketone is employed and is heated with theoil at 150 C. for 3 hours, a soft elastic solid is produced.

Example 11 .--5 parts of zinc bromide dissolved in parts of benzeneyields a viscous oil when heated with the oil at 120 C. for 9 hours.

Example 12.5 parts of naphthalene tetrachloride dissolved in 30 parts ofether yields a sticky elastic mass when heated with the oil at 120 C.for 5% hours.

Example 13.100 parts of linseed oil stand oil are mixed with 5 parts of2:5 dichlorbenzene sulphonic acid dissolved in parts of benzene and themass is heated in vacuo at 100-120 C. for 5 hours. The product is anelastic gel.

Example 14.If the stand oil is treated with 2:5 dichlorbenzene sulphonicacid as such (without the added solvent) under similar conditions tothose described in Example 13, a like product is obtained.

In Examples 5 to 14 ante, instead of linseed oil stand oil, raw ornatural tung oil (wood oil) may be used and converted into a modified,bodied product. Tung oil, in the natural or raw condition, alreadycontains a very high concentration of dispersed phase and is an exampleof a natural isocolloid of that type. Thus it can be modified by thepresent methods without first bodying it to increase the dispersed phasethereof. However this may be done in some embodiments of the presentinvention.

Thus according to the present invention, in the case of wood oil or tungoil, the natural oil as well as a bodied tung oil (wood oil stand oil)may be used. When tung oil is heated in the presence of solvents, as inthe above examples, sudden gelatinization or coagulation to an insolublebody (a characteristic property of tung oil) does not occur. Thus bythe'present methods, I can modify and body tung oil without danger ofsuch coagulation.

In methods such as used in the above examples, wherein a solution ofmodifying agent is added to the oil and the mixture heated, the tung oilis simultaneously modified and bodied, the dispersed phase being bothincreased and modified by the adsorbed polar compound. This occurs whenthe heating is under either reduced or increased pressure, althoughheating under increased pressure to 200 C. or above give greaterbodying. Like bodying also occurs even if the modifying agent isomitted, but in such case no modification other than simple heat-bodyingis obtained.

Thus in some of the present methods, I may first heat-body the tung oilby heating to polymerizing temperature in the presence of a solventunder increased pressure, without gelling it, and then subsequentlymodify the heat-bodied tung oil with the modifying agents as disclosedante with linseed oil, rather than simultaneously modify and heat-bodyit as mentioned ante. As shown in my prior applications, tung oil may beheat-bodied by heating under increased pressure, either with or withoutthe addition of organic solvents. Here too tung oil may be heated] underincreased pressure to obtain a heat-bodied oil which is then treatedwith the polar compound. Also tung oil may be heatbodied by knownmethods, such as heat-bodying a mixture of 3 parts of tung oil and 1part of linseed oil; the presence of the linseed oil preventing thesudden gelatinization or coagulation of the tung oil which wouldotherwise occur when it is heated to 540 F., at atmospheric pressure.Such heat bodied mixed linseed-tung oil product may be used in thepresent methods and modified with the polar compounds, instead oflinseed oil stand oil. Another method to produce heat bodied tung oil isto heat it at comparatively low temperatures, such as e. g. 200 C. andto finish the heating before the danger of gelatinization occurs. Alsoblown tung oil may be used in this process.

Besides bodied fatty oils the following products may form isocolloidssystems with increased concentration of disperse phase and may betreated according to the various embodiments of this invention: estersof polyhydric alcohols containing or consisting of fatty acids, otherthan triglycerides such as fatty oils, (for instance diglycerides,glycol esters, oil modified alkyd resins, rosin or oil modified phenolicresins), synthetic resins containing or consisting of fatty acids, rosinacids or naphthenic acids, metastyrene containing styrene, asphalt.g'oudr'on, pitches, animal and vegetable waxes, etc.

To obtain factises with improved properties, to be used as rubbercompounding ingredients, I heat the modified fatty oil products obtainedaccording to the above described processes with 3 to 25% of sulphur tovulcanizing temperatures. Such temperatures range between and C. Theduration of the procedure is dependent on the starting material andproduct to be obtained. vulcanization accelerators, such asmercaptobenzthiazole, amongst others, may be used and also activators,such as zinc oxide.

In my two-step methods of making modified, bodied fatty oils, I find itadvantageous to produce partially bodied, heat-bodied oils having aviscosity between 0.5 and 1300 centipoises, in the first step thereof;such partially bodied oils being readily adaptable to the second stepwherein they are further modified. Other partially bodied oils such asoxidized oils, blown oils and Voltol oils. (bodied by subjecting the oilto electric potential), etc., having such viscosities are alsoadvantageous.

What I claim is:

1. In the manufacture of bodied products from organic isocolloidscontaining unsaturated carbon compounds, the improved process whichcomprises mixing a partially bodied organic isocolloid containingunsaturated carbon compounds and having a relatively high concentrationof dispersed phase, with a modifying agent capable of facilitating thebodying of said isocolloid and of modifying the properties thereof, andthen heating the mixture to temperatures sufiicient to further body andmodify the partially bodied isocolloid until a modified, heat-bodiedproduct is obtained, said modifying agent being a metalfree organicpolar compound comprising within the molecule an acidic inorganicresidue and an organic residue.

2. The process of claim 1 wherein said modifying agent is an organicsulphonic acid.

3. The process of claim 1 wherein said modifying agent is an organicsulphonyl chloride.

4. In the manufacture of modified, heat-bodied 'oil products from fattyoils, the process which comprises heating the fatty oil to polymerizingtemperatures until a heat-bodied oil product is obtained and then addingto the heat-bodied oil so obtained, a minor amount of an organic polarcompound capable of facilitating the bodying of said fatty oil and ofmodifying the physical and other properties of the heat-bodied fattyoil, and further heating the mixture at polymerizing temperature untilthe organic polar compound is dissolved and a modified heat-bodiedoilproduct is obtained, the said organic polar compound being a metal-freeorganic polar compound comprising within the molecule an acidicinorganic residue and an organic residue and the amount of said organicpolar compound being sufficient to substantially modify the physicalproperties of the heat-bodied oil so obtained.

5. The process of claim 4 wherein said fatty oil-is a drying oil.

6. The process of claim 4 wherein said fatty oil is linseed oil.

7. The process of claim 4 wherein said organic polar compound isaromatic sulphonic acid.

8. The process of claim 4 wherein said organic polar compound is anorganic sulphonyl chloride.

9. The process of claim 4 wherein a current of S02 is passed through thefatty oil during the first heat-bodying.

10. In the manufacture of bodied fatty oils, a two-step method whichcomprises passing a current of S02 through the fatty oil heated topolymerizing temperature until a thickened, heatbodied oil is obtained,and subsequently mixing a minor amount of an organic polar compound withthe heat-bodied oil so obtained and further heating the mixture until amodified heat-bodied oil product is obtained, said organic polarcompound being a metal free organic compound capable of facilitating thebodying of said fatty oil and of modifying the physical and otherproperties of the heat-bodied oil.

11. In the manufacture of modified products from organicisocol1oids,vthe improved processes which comprise mixing an organicisocolloid containing a high concentration of dispersed phase with anorganic polar compound capable of facilitating the bodying of saidisocolloid and of modifying the physical and other properties of theorganic isocolloid and heating the mixture until the organic polarcompound is dissolved in the isocolloid and until a modified product isobtained, said organic polar compound being a metal-free polar organiccompound.

12. The process of claim 11 wherein the mixture is heated totemperatures between and 250 C.

13. The process of claim 11 wherein said organic isocolloid is a fattyoil containing a sufliciently high concentration of disperse phase toproduce substantial modification thereof by simple dispersion of thepolar compound therein.

14. The process of claim 11 wherein said polar compound isbenzenesulphonic acid.

15. The process of claim 11 wherein said polar compound isbenzenesulphonyl chloride.

16. The process of claim 11 wherein said organic isocolloid is a linseedoil stand oil.

LASZLO AI'JER.

